Polymerization of acetylenes

Abstract

A process for the polymerization of actylenically unsaturated compounds by contacting the monomer(s) under polymerization conditions with a catalyst system comprising: a) a source of cations of one or more Group VIII metals; b) a bidentate ligand containing phosphorus, arsenic and/or antimony; and c) a source of anions.

What is claimed is: 
     
       1. A process for the polymerization of acetylenically unsaturated compounds by contacting at least one acetylenically unsaturated compound under polymerization conditions with a catalyst system comprising: a) a source of cations of at least one Group VIII metal selected from the group consisting of cations of palladium, rhodium, or mixtures thereof;   b) a bidentate ligand comprising phosphorus, arsenic and/or antimony; and   c) a source of anions.   
     
     
       2. The process of claim 1 wherein the catalyst system comprises palladium cations. 
     
     
       3. The process of claim 1 wherein the bidentate ligand is of the formula   R.sup.1 R.sup.2 M.sup.1 RM.sup.2 R.sup.3 R.sup.4           (I)     wherein each of M 1  and M 2  are independently a phosphorus, arsenic or antimony atom, each of R 1 ,R 2 ,R 3  and R 4  are independently a substituted or non-substituted hydrocarbyl group and R is a bivalent organic bridging group having from 2 to 6 atoms in the bridge.   
     
     
       4. The process of claim 3 wherein M 1  and M 2  are both phosphorus atoms. 
     
     
       5. The process of claim 3 wherein R 1 , R 2 , R 3  and R 4  are the same or different substituted or non-substituted aliphatic groups having form 1 to 10 carbon atoms. 
     
     
       6. The process of claim 3 wherein at least one of R 1 ,R 2 , R 3  and R 4  is a tertiary alkyl group having from 4 to 10 carbon atoms. 
     
     
       7. The process of claim 3 wherein at least one of R 1 ,R 2 , R 3  and R 4  is a tertiary butyl group. 
     
     
       8. The process of claim 3 wherein R is a bivalent organic bridging group containing from 2 to 4 atoms in the bridge at least 2 of which are carbon atoms. 
     
     
       9. The process of claim 8 wherein R is a group --CH 2  --CH 2  --CH 2  --. 
     
     
       10. The process of claim 1 wherein the source of anions is selected from the group consisting of water, one or more alkanols, one or more carboxylic acids, and mixtures thereof. 
     
     
       11. The process of claim 10 wherein the source of anions is an alkanol having from 1 to 8 carbon atoms. 
     
     
       12. The process of claim 10 wherein the source of anions is a carboxylic acid having a pKa of less than about 6. 
     
     
       13. The process of claim 12 wherein the source of anions is a carboxylic acid having a pKa of less than about 2. 
     
     
       14. The process of claim 1 wherein the acetylenically unsaturated compound is of the formula HC.tbd.C--X wherein X represents hydrogen or a substituted or non-substituted hydrocarbyl group. 
     
     
       15. The process of claim 14 wherein X is hydrogen. 
     
     
       16. The process of claim 14 wherein X is a phenyl group. 
     
     
       17. The process of claim 14 wherein X is a hydroxyl-substituted hydrocarbyl group. 
     
     
       18. The process of claim 14 wherein X is an isopropenyl, a hydroxymethyl or a 1-hydroxyethyl group. 
     
     
       19. The process of claim 1 wherein the polymerization is carried out at a temperature within the range of about 0° to about 150° C. 
     
     
       20. The process of claim 19 wherein the polymerization is carried out at ambient temperature. 
     
     
       21. The process of claim 1 wherein the polymerization is carried out at a pressure within the range of about 0.1 to about 20 bar. 
     
     
       22. The process of claim 1 wherein the polymerization is carried out in the presence of a solvent. 
     
     
       23. The process of claim 22 wherein the solvent is N-methylpyrrolidone. 
     
     
       24. The process of claim 22 wherein the solvent is methanol.